Polyesteramides prepared by reacting beta-propiolactone with an aziridine salt, a polycarboxylic acid, and a polyhydric alcohol

ABSTRACT

An improved polyesteramide is produced by reacting betapropiolactone with an aziridine salt represented by the structural formula:   WHERE R1, R4, R5 and R6 have the meanings given above.   WHERE R4 has the meaning given above. The above diacid may then be reacted with beta-propiolactone, the polycarboxylic acid and the polyhydric alcohol to form an improved polyesteramide containing repeating units which may be represented by the structural formula   WHEREIN R1 has the meaning given above, to yield a diacid represented by the structural formula   WHEREIN R1 has the meaning given above; R4 represents a divalent radical such as aminoalkyleneoxy or oxyalkyleneamino; R5 represents a divalent radical such as alpha-beta ethylenically unsaturated alkylidene; and R6 represents a divalent radical such as alkylene or alkylidene. The above aziridine salt may also be reacted with an acid represented by the structural formula   WHEREIN R1 represents a divalent radical such as alkylene, arylene, or aralkylene, wherein one or all of the hydrogen atoms thereof can be substituted with F, Cl, Br, lower alkyl and/or lower alkoxy; and where R2 and R3 represents monovalent radicals such as hydrogen, alkyl, or aryl; AND WITH A POLYCARBOXYLIC ACID, SUCH AS MALEIC OR DIMER ACID, AND WITH A POLYHYDRIC ALCOHOL, SUCH AS CASTOR OIL OR 1,6-HEXANE DIOL; THE THUS FORMED POLYESTERAMIDE CONTAINS REPEATING UNITS WHICH MAY BE REPRESENTED BY THE STRUCTURAL FORMULA:

nited States Patent 1 1 Christena et al.

[4 1 Jan. 22, 1974 Vulcan Materials Company, Birmingham, Ala.

Filed: Oct. 20, 1971 App]. No.: 190,819

[73] Assignee:

[52] US. Cl 161/195, 260/18 R, 260/18 N, 260/22 R, 260/75 N, 260/78 R,260/78 UA,

[51] Int. Cl C08g 20/30 [58] Field of Search... 260/18 N, 22 R, 75 N, 78R,

260/78 UA, 868, 869, 873, 18 R, 22 CB; 161/195 [56] References CitedUNlTED STATES PATENTS 3,676,424 7/1972 Christena et a1 260/75 3,676,2917/1972 Christena et a1 260/75 2,887,468 5/1959 Caldwell et al. 260/753,546,178 12/1970 Caldwell et a1... 260/75 2,463,977 3/1949 Kropa 260/783,475,385 10/1969 Goodman et al. 260/75 3,502,602 3/1970 Helm et al.260/22 3,660,327 5/1972 Loncrini et a1... 260/22 3,674,727 7/1972 Fekete260/22 2,806,822 9/1957 Ott 260/2.5 2,779,701 1/1957 Robitschek et a1.260/75 3,262,991 7/1966 McClendon et al. 260/75 3,354,126 11/1967 Ham etal. 260/78 3,642,712 2/1972- Sambeth et a1... 260/78 2,946,769 7/1960Rose et a1 260/75 3,422,116 l/1969 Frazer 260/78 Primary ExaminerDonaldE. Czaja Assistant Examiner-Eugene C. -Rzucidlo Attorney, Agent, orFirm-Peter l-l. Smolka et al.

[57] ABSTRACT An improved polyesteramide is produced by reactingbeta-propiolactone with an aziridine salt represented by the structuralformula:

wherein R represents a divalent radical such as alkylene, arylene, oraralkylene, wherein one or all of the hydrogen atoms thereof can besubstituted with F, Cl, Br, lower alkyl and/or lower alkoxy; and where Rand R represents monovalent radicals such as hydrogen, alkyl, or aryl;and with a polycarboxylic acid, such as maleic or dimer acid, and with apolyhydric alcohol, such as castor oil or 1,6-hexane diol; the thusformed polyesteramide contains repeating units which may be representedby the structural forn ula O O O O O l wherein R has the meaning givenabove; R represents a divalent radical such as aminoalkyleneoxy oroxyalkyleneamino; R represents a divalent radical such as alpha-betaethylenically unsaturated alkylidene; and R represents a divalentradical such as alkylene or alkylidene. The above aziridine salt mayalso be reacted with an acid represented by the structural formula 0 0II g 110 c-won,

wherein R has the meaning given above, to yield a diacld represented bythe structural formula where R, R, R and R have the meanings givenabove.

10 Claims, No Drawings POLYESTERAMIDES PREPARED BY REACTINGBETA-PROPIOLACTONE WITH AN AZIRIDINE SALT, A POLYCARBOXYLIC ACID, AND APOLYHYDRIC ALCOHOL BACKGROUND OF THE INVENTION 1. Field of the InventionThis invention relates to polyesteramides.

2. Summary of the Prior Art Since their discovery, synthetic resins orpolymers such as the polyamides, polyesters, and polyesteramides havefound application in industries and scientific disciplines in many formssuch as coatings, shaped articles and binders. See, for example, U. S.Pat. Nos. 2,463,977, 2,490,00l005, 2,495,172, 2,523,999, 2,806,822,3,036,974 and 3,354,!26; and French Patent No. 1,547,058. However, thesearch has continued, particularly in the area of glass fiber-reinforcedplastic articles, for ways to produce polymers which are resistant toexisting and anticipated destructive ele ments and forces to beencountered in their environments. For example, new ways are needed toproduce polymers suitable for use in fire-retardant coatings, and impactresistant glass fiber-reinforced plastic articles such as boat hulls,where adhesiveness or bonding between the glass fibers and the polymermatrix is important.

In three prior. copending applications which are assigned to theassignee of the present invention, polyesteramides and processestherefor are described which are useful, for example, in the area ofglass fiberreinforced plastic articles or laminates. In this area, glassfibers are typically mixed or coated with a thermosetting bindercomposition comprising a thermoset- 4O ting unsaturated polymer and avinylic cross-linking agent such as styrene. Desirably, thethermosetting polymer forms a stable solution with styrene forapplication and storage purposes, and the thermosetting polymer shouldalso have good impact strength after 4 curing. The present invention wasmade as a result of the search for polyesteramides having improvedsolubility in vinylic cross-linking agents such as styrene and havingimproved impact strength after curing.

SUMMARY OF THE INVENTION Accordingly, a general object of the presentinvention is to provide polymers having desired characteristies asdiscussed above.

Another more particular object of the present invencan be r presented bythe structural formula 0 o'- 0 o o is provided. I

In this and in the below given structural formulas, R represents adivalent radical which may be alkylene, arylene, or aralkylene, whereinone or all of the hydrogen atoms thereof can be substituted with one ormore .q it s e? ft m theammnsistirep Cl...

Br, lower alkyl and lower alkoxy; R and R represent monovalent radicalswhich may independently be selected from the group consisting ofhydrogen, alkyl, and aryl; R represents a divalent radical which may beaminoalkyleneoxy or oxyalkyleneamino; R represents a divalent radicalsuch as alpha-beta ethylenically unsaturated alkylidene, and Rrepresents a divalent radical such as alkylene or alkylidene.

In accordance with another aspect of the present invention, apolyesteramide having repeating units which can be represented by thestructural formula 0 o 0 o 0 tttto im ioLatolLllolmrcml l L l L J L l Lis provided. In this structural formula, R, R, R and R have the meaningsgiven above.

In accordance with another aspect of the present invention, a process isprovided for producing polyesteramides. This process involves reacting:

A. at least one member of the group consisting of an aziridine saltwhich may be represented by the structural fonnula or a diacid which maybe represented by the structural formula ll 1 i O HOG-R -R d-R loH B. apolycarboxylic acid or an acid anhydride thereof:

C. a polyhydric alcohol; and

D. beta-propiolactone.

In accordance with yet another aspect of the present invention, theabove process further includes additionally reacting a dicarboxylic acidof the formula HOOCR'COOH.

A primary feature of the above aspects of the present invention is thediscovery that the use of betapropiolactone in the production of thesenovel polyesteramides results in improved solubility in vinyliccrosslinking agents such as styrene and in improved impact strength inthe cured polymer.

These and other aspects and advantages of the present invention will bemore fully apparent to one skilled in the art from the followingdescription of the preferred embodiments:

DESCRIPTION OF THE PREFERRED EMBODIMENTS The Aziridine Salt Theaziridine salts which may be used to prepare the polyesteramides may berepresented by the general formula:

R represents a divalent organic radical such as alkylene, arylene, oraralkylene, wherein one or all of the hydrogen atoms thereof can besubstituted with one or more members selected from the group consistingof F,

Cl, Br, lower alkyl, and lower alkoxy. R and R- represent monovalentorganic radicals which are independently selected from the groupconsisting of hydrogen, alkyl, and aryl. The alkyl and alkylene groupsor portions of the groups may contain, for example, from one to carbonatoms.

In one preferred embodiment of the present invention R' is loweralkylene or phenylene, R is hydrogen or methyl and R is hydrogen.

In another preferred embodiment of the present invention wherein thesalts are especially useful to produce flame retardant polyesteramidesas described more completely below, R is tetrachlorophenylene,tetrabromophenylene, or a radical represented by the structural formulaby which is meant the residue of l,4,5,6,7,7- hexachlorobicyclo[2.2.l1-5-heptene-2,3-dicarboxylic acid commercially available as chlorendicacid under the Het Acid trademark of Hooker Chemical Corporation. Inthis embodiment R is hydrogen or methyl and R is hydrogen.

The aziridine salts may be produced by co-reacting at least onedicarboxylic acid represented by the general formula:

II II no 041 -0011 with at least one aziridine compound represented bythe general formula:

wherein R,R and R may have the above described meanings.

The above represented dicarboxylic acids should be free of non-benzenoidunsaturation, in order to inhibit undesirable reactions with theaziridine compound. For example, maleic acid is not within the scope ofsuch acids. And unlike many reactions employing dicarboxylic acids, inthis reaction the acid anhydrides are not equivalents and the term acidemployed in connection with the dicarboxylic acids is meant to refer tothe acid containing two carboxyl groups and not to the correspondinganhydride.

Non-limiting examples of suitable dicarboxylic acids include amongothers malonic acid, succinic acid, glutaric acid, adipic acid, azelaicacid, brassylic acid, phthalic acid, terephthalic acid, isophthalicacid, 1,8- naphthalenedicarboxylic acid, araliphatic dicarboxylic acidssuch as p,p' benzophenonedicarboxylic acid, and 3-methyl phthalic acid,hemipic acid, 3-bromophthalic acid, 4-chloroisophthalic acid,tetrabromophthalic acid, tetrachlorophthalic acid, and chlorendic acid.

Non-limiting examples of suitable aziridine compounds include amongothers ethyleneimine (aziridine), 2-methyl aziridine, 2-phenylaziridine, 2,2- dimethyl aziridine, 2-benzyl aziridine and 2-dodecylaziridine. Ethyleneimine is preferred because of cost, availability, andreactivity, although 2-methyl aziridine has also been found to besuitable for certain specialized applications.

The reaction between the dicarboxylic acid and the aziridine compound ismost conveniently affected by simply adding the aziridine compound tothe acid at any convenient temperature, but generally between 20 and Cand preferably between 0 and 50C. At lower temperatures, the reactionproceeds at an uneconomically slow rate whereas at higher temperaturesthe salt tends to rearrange to an amino ester or hydroxy amide. Thereaction is preferably conducted in the presence of a suitable solventwhich is inert to the acid and the aziridine compound. Examples ofsuitable solvents include among others ethanol, methanol, xylene,dioxane, toluene, chlorobenzene, ethylene dichloride, and acetone, whichis preferred. The solvent can be present in any amount up to infinitedilution. The aziridine compound is preferably added to the acid in amolar ratio of 10:10 although slightly varying molar ratios such as 10:1I to l 1:l0 can also be employed. At lower molar ratios insufficientaziridine is present in order to completely convert the acid to theaziridine salt whereas at greater ratios competing side reactions occurundesirably reducing the yield of the salt.

The Diacid HOOCRCORCOR'COOH The diacids which may be used to prepare thepolyesteramides may be represented by the general formula R has themeaning given above, and R represents a divalent organic radical such asaminoalkyleneoxy or oxyalkyleneamino. The alkylene portions of thegroups may contain, for example, from two to 15 carbon atoms.

R is preferably tetetrachlorophenylene, tetrabromophenylen'e, or theradical represented by the structural formula In this embodiment, R ispreferably aminoethylenoxy, oxyethyleneamino, aminoisopropyleneoxy oroxyisopropyleneamino, i.e., R may be represented by the general formulaswhere R is hydrogen or methyl. In the most preferred embodiment, R isaminoethyleneoxy or oxyethyleneamino, i.e., R is hydrogen.

The diacid is preferably produced by coreacting at least one of theabove discussed aziridine salts with at least one of the above discusseddicarboxylic acids represented by the general formula HOOCRCOOH.

The reaction between the aziridine salt and the dicarboxylic acid ismost conveniently effected by simply adding or mixing the aziridine saltwith the dicarboxylic acid at any convenient temperature at which thereaction proceeds at a measurable rate. Typically, this temperature isbetween about 0 and 200C, preferably between about 40 and 180C. Thereaction may be conducted in the presence of a suitable solvent which isinert to the aziridine salt and the dicarboxylic acid. Examples ofsuitable solvents include among others toluene, dioxane, xylene andacetone. The solvent may be present in any amount up to infinitedilution. The aziridine salt is preferably reacted with the carboxylicacid is substantially stoichiometric proportions, i.e., at a molar ratioof 10:10, although slightly varying molar ratios such as 10:11 to 11:10may also be employed. The Polycarboxylic Acid or Anhydride thereof Asindicated above, in the present invention there is provided an improvedprocess for producing polyesteramides comprising coreacting theaziridine salt and/or the diacid with at least one polyhydric alcohol,betapropiolactone, and at least one polycarboxylic acid orpolycarboxylic acid anhydride thereof.

In the broadest aspect of the present invention any polycarboxylic acidor anhydride thereof can be employed. However, dicarboxylic acids andanhydrides elude among others glutaconic acid, itaconie acid, citraconicacid, mesaconic acid, fumaric acid and maleic acid which is preferred.Dimer acid, typically produced by dimerization of unsaturated fattyacids at midmolecule and usually containing 36 carbon atoms, may also beused, particularly in combination with maleic acid or anhydride, andparticularly where even further improvement in impact strength of theresulting polyesteramide is desired. Tri-or higher functional acids suchas trimesic acid can be employed when it is desired toproduce a branchedor cross-linked polyesteramide. The Polyhydric Alcohol In the broadestaspects of the present invention, any polyhydric alcohol can be employedalthough the dihydric alcohols are preferred when it is desired toproduce linear polyesteramides.

Typically, the diliydrie alcohols have from two to six carbon atoms.

Examples of suitable polyhydric alcohols include among others ethyleneglycol, diethylene glycol, 1,2- propylene glycol, dipropylene glycol,1,3-propylene glycol, 1,3-butylene glycol, 1,2-butylene glycol,neopentyl glycol, 1,3-pentanediol, 1,2-butenediol, 1,5- pentanediol, and1,6-hexanediol. Particularly preferred are the alkanediols of from 5 to6 carbon atoms, insofar as the longer chain diols have been found togive im' proved impact strength. Higher polyhydric alcohols such astrimethylol propane and pentaerythritol can be used in minor amountswhich do not materially alter the linear nature of the polyesteramide.

Castor oil, which is chiefly ricinolein, is another polyhydric alcoholwhich may be used, and can be especially advantageous where even furtherimprovement in impact strength of the resulting polyesteramide isdesired.

Beta-Propiolactone As indicated above, beta-propiolaetone is used in thepresent invention for the production of polyesteramides. Of course,beta-propiolactone,

is well known per se and its production or derivation is not part of thepresent invention. Polyesteramide Production The following generalizedequation illustrates the reaction which is thought to occur in forming apolyesteramide by reacting the aziridine salt, an alpha, betaunsaturateddicarboxylic acid, a dihydric alcohol and beta-propiolactone:

thereof are preferred when it is desired to produce linearpolyesteramides. Examples of certain dicarboxylic acids free ofnon-benzenoid unsaturation are given above. Their correspondinganhydrides such as phthalic anhydride can also be employed. In anespecially preferred embodiment of the present invention, thedicarboxylic acid or anhydride is alpha-beta ethylenically unsaturatedin order to render the polyesteramide cross-linkable with a vinylmonomer. Examples of suitable alpha-beta unsaturated dicarboxylic acidsin- R, R", R and R have the meanings given above; R represents adivalent organic radical such as alpha-beta ethylenically unsaturatedalkyldene; and R represents a divalent organic radical such as alkyleneor alkylidene.

Preferably, R is a divalent organic radical represented by the formulawhere R is hydrogen or lower alkyl, preferably methyl. been removed ormore preferably until the acid num- R is most preferably hydrogen. berof the reaction mixture has dropped to a value Preferably, R is loweralkylene or lower alkylidene. below 100 and preferably below 50 and alsountil the The following generalized equation illustrates the reaminenumber of the reaction mixture has dropped to action which is thought tooccur in forming a polyestera alue below and preferably below 10. amideby reacting the aziridine salt, a dicarboxylic acid Th ti i u uall onduted in the presence of HOOCR'COOH (which together are thought to reactan inert atmosphere of nitrogen, argon or the like, in itu t0 t'OTm thediacid HoocRlcoRcoRlcooH), under substantially oxygen-free conditions,i.e., an atan alpha, beta-unsaturated dicarboxylic acid HOOCR- mosphei-econtaining l h 20 ppm oxygen d SCOOH, a dihydric alcohol HORGOH, andbeta- 10 preferably less than 10 ppm oxygen. The reaction ispropiolactone; 7 W conveniently conducted at atmospheric pressure, butif if I /o-m not'i-m-boum i noooiuooon nooowcoon HomoH (Emma-q on: x

o o o o o o 0 r1 "TF1" lflf ilflf 1 I -0o-it -oiu--o-w-o0-R oomoo-m-ocH,oiIit L eli- J A o J L-W... 4 R, R R, R, R and R have the meaningsgiven desired may be conducted at superatmospheric or subabove.atmospheric pressures, and in a batch, semi- The brackets in the aboveformulas are meant to indicontinuous, or continuous manner. cate alinear polymer having recurring ester and amide Polyesteramides producedin accordance with that linkages in the backbone thereof. The bracketsare not preferred embodiment of the present invention emmeant toindicate that the reactants which produce ploying an alpha-betaethylenically unsaturated acid these recurring units must necessarily bepresent in the can be cross-linked with copolymerizable vinyl monomostpreferred equimolar ratio. mers, sometimes referred to as vinyliccross-linking The polyesteramides are produced by combining the ag nts,coreactants in a reaction vessel and heating it to any Examples ofsuitable vinyl monomers include among temperature at which the reactionproceeds at an ecoothers vinyl toluene, acrylic acid, methyl acrylate,2- nomical rate. This is generally between zero and 200 ethylhexylacrylate, acrylonitrile, methyl methacrylate, C and preferably between40 and 180 C. When it is n-butyl acrylate, mono-chlorostyrene, ethylacrylate, desired to achieve a high molecular weight, the ratio of ethylmethacrylate, acrolein, vinyl acetate, vinylidene the polycarboxylicacid to the polyhydric alcohol may chloride, vinyl chloride, vinylbromide, and styrene be critical and generally is between 15:10 and10:15 which is preferred because of costs, availability and reandpreferably between 1 1:10 and 10:1 1. The aziridine activity and thefact that it does not adversely affect the salt and the diacidHOOCR'CORCORCOOH may be physical properties of cured compositions ofthese employed in somewhat more widely varying molar rapolyesteramides.The polyesteramide and the vinyl tios, but are generally present in amolar ratio of 10:1 40 monomer can be mixed in widely varying weightratios to 1:10 and preferably 3:1 to 1:3 moles of salt or diacid ch as1:10 to 10;] but are preferably combined in raper mole of dicarboxylicacid HOOC CO The tios of 3:1 to 1:3. In a preferred embodiment of themolar ratio of beta-propiolactone to aziridine salt or present inventionh i h mixture of i diacid may range from about l0;l00 to 100210, moremide and vinyl monomer when cured must be flame retypically from about10:20 to 20:10, and preferably tardant the polyesteramide and the vinylmonomer are from about 10:15 to 15110. in that pref rre embodimixed in aquantity such that the halogen content of the ment of the presentinvention wherein the polyesteramixture is greater than 10 andpreferably greater than mides are intended to be self-extinguishing, asalt of a 20 ight er ent,

chlorinated or brominated acid is employed in an In order to assist inthe maintenance of the stability amount such that the totalpolyesteramide or its mixof the mixture of the polyesteramide and vinylmonoture with a Vinyl monomer has a halogen content of mer, aconventional free radical trap such as hydroquigreater than 10 weightpercent and preferably greater none may b d. In order to cure thesecompositions, than 20 weight percent. The reactants can be charged a frradical initiator such as benzoyle peroxide, sequentially o he vesselbut ad antag y y be methyl ethyl ketone peroxide orazobisisobutyronitrile charged simultaneously in order to pr a random isadded to the mixture. Accelerators such as cobalt polyesteramide andmaximize molecular Weight, thus naphthenate can also be employed as iswell known in resulting in greater impact strength for the polyesterathean mide. When the reactants are not charged simulta- The Polyesteramidesf the present invention espeneously, the diacid HOOCR'CORCORCOOH isprefcially when mixed with the above-described vinyl erahly used in lieuof the aziridine salt, and most prefermonomers provide a cross-linkablecompositions ably is generated or produced in situ from the aziridinewhich, in view of its wetting ability and adhesiveness,

Salt, 80 35 again to maXimiZe molecular ght a d imand resulting impactstrength, is especially useful in adpact strength. The use of thediacid, either by generathesivesand coatings, and as binders for thebonding of ing it in situ or by adding it directly to the reaction zoneglass fibers and glass fiber laminates in glass fiberhas also been foundto improve color and storage stareinforced shaped articles. When soused, it provides bility of the resulting polyesteramides. The reactionis an effective substitute for polyester resins commonly continued untila stoichiometric amount of water has employed for such purposes in thepast.

It will also be apparent that various modifying agents such as fillers,e.g., carbon black, talc, etc. as well as heat and light stabilizers,dyes, and pigments may be incorporated into the polyesteramides withoutdeparting from the scope of the invention.

Amine Number is used herein to refer to the value determined as follows:

Weigh out 1 to 2 g of polyesteramide in 200 ml Erlenmeyer flask. Addapproximately 50 ml glacial acetic acid'and dissolve sample. Titratewith 0.1 N HClO using one drop of one percent crystal violet in glacialacetic acid as indicator. Titrate to first permanent green color. AmineNumber [10.046 (ml 0.1 N HClOQl/[Grams Sample] Acid Number is usedherein to refer to the value determined as follows:

Weigh out 1 to 2 g of polyesteramide in 200 ml Erlenmeyer flask with 25ml acetone. Titrate with 0.1 N Alcoholic KOl-l using phenolphthaleinindicator.

Acid Number [5.61 (m10.1 N Alcoholic KOH)]/[Grams Sample] The inventionis further illustrated by the following examples; all ratios, parts andpercentages in the examples, as well as in other parts of thespecification and claims, are by weight unless otherwise indicated.These non-limiting examples are illustrative of certain embodimentsdesigned to teach those skilled in the art how to practice the inventionand to represent the best mode contemplated for carrying out theinvention.

EXAMPLE I This example illustrates the synthesis of a salt of theformula To a three-neck, 2-liter flask equipped with stirrer,thermometer, dropping funnel, and cooling bath was added 388.87 g (1.00mole) of chlorendic acid in 1200 ml very dry acetone. To the above wasadded 43.07 g (1.00 mole) of ethylenimine dropwise at such a rate thatthe temperature was 1620C. When about half the ethylenimine was added,the solid salt started to precipitate out. After all evidence ofexotherm disap-- peared, the solids were filtered off and air dried atroom temperature in a hood, follwed by drying in a vacuum oven atambient temperature to give a white solid, mp. l49-1 50C yield 98.9percent.

Amine equivalent calcd. for C H,,Cl NO :-43 l .91

found: 434 Carboxyl equivalent calcd. for C H Cl NO 215.95 found: 213The salt was stored at C to prevent gradual rearrangement to themono-2-aminoethyl chlorendate.

EXAMPLE II This example illustrates the synthesis of a salt of theformula Using equipment as in Example 1, 332.3 g (2 moles) phthalic acidand 2900 ml very dry acetone were charged to a pot. To this was added86.1 g (2 moles) ethylenimine, dropwise at 16- 20C. The reaction mixturewas filtered to give a white solid after air and vac uum drying, atambient temperature m.p. 94-95C, yield 95.7 percent.

Amine equivalent calcd. for C H NO 209.20

found: 210.50 Carboxyl equivalent calcd. for C, H, NO,,:

found: 102.40

EXAMPLE 111 This example illustrates the synthesis of a salt of theformula Using equipment as in Example 1, 332.3 g (2 moles) ofisophthalic acid was mixed with 2500 ml dry acetone and 500 ml drymethanol. To this was added 86.1 g (2 moles) ethylenimine dropwise at 1620C. The reaction mixture was filtered to give a white solid afterainbient temperature air and vacuum drying, m.p. C.

Amine equivalent calcd. for C H NO 209.20

found: 209.20 Carboxyl equivalent calcd. for C, H,,NO.,:

found: 107.40 The above salt contained a substantial amount ofimpurities due to poor solubility of isophthalic acid in the acetonemethanol mixture as indicated by large melting point range.

i if Hoc- 00- EXAMPLE IV This example illustrates the synthesis of asalt of the formula Using equipment as in Example 1, 332.3 g (2 moles)of terephthalic acid was slurried with 2500 ml dry acetone and 500 m1dry methanol. To this was added 86.1 g (2 moles) ethylenimine, dropwiseat 16 20C. The reaction mixture was filtered to give a white solid afterambient temperature air and vacuum drying, m.p. 184 210C.

Amine equivalent calcd. for C I-I NO 209.20

found: 234.9 Carboxyl equivalent calcd. for C H NO found: 109.20 Theabove salt contained a substantial amount of impurities due to poorsolubility of the acid in the acetonemethanol mixture as indicated bythe large melting point range.

EXAMPLE V This example illustrates the synthesis of a salt of theformula Using equipment as in Example l, 77.24 g (0.52 mole) adipic acidwas dissolved in 600 ml dry acetone. To this was added 22.76 g (0.52mole) ethylenimine, dropwise at 17 23C. The reaction mixture wasfiltered to give a white solid after ambient temperature air and vacuumdrying, m.p. 68.5 690C, yield 94.4 percent.

Amine equivalent calcd. for C H, NO 189.21

found: 196.85 Carboxyl equivalent calcd. for C H, NO,,: 94.60

found: 96.65

EXAMPLE VI This example illustrates the synthesis of a salt of theformula C Cl EXAMPLE VII This example illustrates the synthesis of asalt of the formula The procedure of Example VI is repeated employingthe same conditions, times and ingredients except that thetetrachlorophthalic acid hemihydrate is replaced by an equimolar amountof tetrabromophthalic acid hemihydrate.

EXAMPLE VIII Preparation of a Polyesteramide Using the Mono Salt ofChlorendic Acid and Ethylenimine, Additional Chlorendic Acid; MaleicAnhydride; 1, 6-Hexane Diol; Propylene Glycol; andBeta-PropiolactonePreparation of the polyesteramide was accomplished in a conventionalreactor equipped with thermometer, stirrer, full condenser, partialcondenser to contain glycol vapors, nitrogen sparge and source ofvacuum.

The general procedure used to prepare the polyesteramide was to chargethe diol, the glycol, and maleic anhydride to the reactor along withxylene as an azeotroping agent. After commencement of stirring andgradual heating, chlorendic acid, beta-propiolactone and the salt wereadded in that order, and reaction was evidenced by a rapid exothermafter which stage all materials were in liquid form. With thetemperature further elevated, water was azeotropically distilled over asthe reaction proceeded. Vacuum was then applied to remove excess glycol,remaining water and xylene. After this, vacuum was removed; the productwas cooled and styrene and inhibitor was added to give a 60 85 percentsolution of the polyesteramide in styrene. The final liquid productcould be cured to a solid at elevated temperature using a free radicalcuring agent such as benzoyl peroxide or at room temperature usingcobalt napthenate and methyl ethyl ketone peroxide.

The specific procedure was as follows: To the reactor, using a nitrogenblanket, was charged 139.20 g (1.17 moles) 1,6-hexane diol, and 29.90 g(0.39 moles) propylene glycol along with 102.70 g (1.04 moles) of maleicanhydride, in xylene. Stirring and heating were commenced and, after a30-minute period, 203.60 g (0.52 moles) chlorendic acid were added at C.After allowing the temperature to rise to 132C, the reactor contentswere cooled to 50C and 26.00 g (0.36 moles) beta propiolactone wereadded followed by addition of 226.10 g (0.52 moles) chlorendicacidethylenimine salt at C. Exotherming occurred and stirring wascontinued over a six-hour period as the temperature rose to a maximum of166C. Vacuum (5 mm) was applied and any remaining water, glycol, andxylene distilled over. Vacuum was removed, and at about 160C, the moltenresin was transferred to 270 g styrene containing 135 mg monotertiarybutylhydroquinone yielding 934 g of a 71.10 percent solution of thepolyesteramide in styrene.

A sample was cured using 0.3 percent cobalt naphthenate and 1.7 percentLupersol DDM methyl ethyl ketone peroxide solution (60 percent methylethyl ketone peroxide in dimethyl phthalate). Final Acid Number was30.0; Final Amine Number was 2.1; Molecular Weight was 1466; and Impact(2 lb. wt.) was 43 inches. Using 0.3 percent cobalt naphthenate and 1.0percent Lupersol DDM methyl ethyl ketone peroxide solution gave animpact of 26 inches to a cured sample after 16 hours cure at about 25C.

It was noted that no precipitate formed in the polyesteramide styrenesolution on standing at about 25C as was observed in comparable runswhich were conducted without using beta-propiolactone. This improvedresin solubility in styrene is thought to be attributable to thebeta-propiolactone. Further, the molecular weight and impact values werealso higher than was observed in comparable runs which were conductedwithout using beta-propiolactone.

EXAMPLE IX Preparation of a Polyesteramide Using the Mono Salt ofChlorendic Acid and Ethylenimine; Maleic Anhydride; l, 6-Hexane Diol;and Beta-Propiolactone Using the apparatus and general procedure as inExample VIII, 157.02 g (1.32 moles) 1,6-hexane diol and 124.08 g (1.26moles) maleic anhydride were charged under a nitrogen blanket to 250 mlxylene in the reactor. With heating and stirring the temperature rose to72C over a one-hour period. The temperature was reduced to 35C and 45.60g (0.63 moles) betapropiolactone added. With continued heating thetemperature rose to 101C over a two-hour period. At this point 273.30 g(0.63 moles) chlorendic acidethylenimine salt were added. With furtherreaction, the temperature rose to 164C over a five-hour period. Vacuum(6mm) was applied and any remaining water, glycol, or xylene wasdistilled over. Vacuum was removed and, at about 160C, the molten resinwas transferred to 260 g styrene containing 172 mg toluohydroquinoneyielding 828 g of a 70.00 percent solution of the polyesteramide instyrene.

A sample was cured for 67 hours at about 25C using 0.2 percent cobaltnaphthenate and 3.0 percent Lupersol DDM methyl ethyl ketone peroxidesolution. Final Acid Number was 35.0; Final Amine Number was 4.0;Molecular Weight was 1165; and Impact (2 lbs), was 23 inches.

EXAMPLE x Using the apparatus and general procedure as in Example VIII,1 15.3 g (1.17 moles) maleic anhydride and 89.52 g (1.29 moles)propylene glycol were charged under a nitrogen blanket to the reactor.The mixture was heated with stirring for one hour at 78C. At 60C, 56.52g (0.78 moles) beta-propiolactone was added. The temperature rose to 82Cover a 1% hour period. At this point, 338.64 g (0.64 moles) chlorendicacidethylenimine salt were added. With further reaction, the temperaturerose to 158C over a five-hour period. Vacuum mm) was applied and anyremaining glycol and water distilled over. Vacuum was removed and, atabout 160C, the molten resin was transferred to 257 g styrene containing172 mg toluohydroquinone yielding 830 g of a 70.00 percent solution ofthe polyesteramide in styrene. I

A sample was cured for 48 hours at about 25C using 0.2 percent cobaltnaphthenate and 3.00 percent Lupersol DDM methyl ethyl ketone peroxidesolution. I

Final Acid Number was 35.8; Final Amine Number was 4.1; Molecular Weightwas 1180; and Impact (2 lb), was eight inches. A similar resin made withno betapropiolactone would have a molecular weight in the range of650-800. Impact would be two to three inches.

EXAMPLE XI 5 Preparation of a Polyesteramide Using the Mono Salt ofChlorendic Acid and Ethylenimine; Maleic Anhydride; Castor Oil; andBeta-Propiolactone Using the apparatus and general procedure as inExample VIII, 261.18 g (0.28 moles) castor oil (Baker U.S.P.) and 55.20g (0.56 moles) maleic anhydride were charged under a nitrogen blanket tothe reactor. With heating and stirring, the temperature rose to 92C overa 1% hour period. The temperature was lowered to 34C and 40.56 g (0.56moles) beta-propiolactone added. Reaction was continued for 1% hours at78C. At this time, 243.06 g (0.56 moles) chlorendic acidethyleniminesalt were added. The temperature rose to 176C maximum over a reactiontime of three hours. Vacuum (6 mm) was applied and any remaining water,glycol, or xylene distilled over. Vacuum was removed and, at about 175C,the molten resin was transferred to 1 16 g styrene containing 143 mgtoluohydroquinone yielding 593 g of an 84.00 percent solution of thepolyesteramide in styrene.

A sample was cured using 0.2 percent cobalt naphthenate and 3.00 percentLupersol DDM methyl ethyl ketone peroxide solution. Final Acid Numberwas 30.2; Final Amine Number was 3.0; Molecular Weight was 1270; andImpact (2 lbs) was 35 inches. The impact data was obtained by allowingthe sample to cure for six days at about 25C. Alternatively, curing maybe effected by heating the sample at, for example, 107C for 45 minutes.

EXAMPLE XII Using the apparatus and general procedure as in ExampleVIII, 109.50 g (1.43 moles) propylene glycol, 445.65 g (0.48 moles)castor oil (Baker U.S.P.) and 211.80 g (2.15 moles) maleic anhydridewere charged under a nitrogen blanket to the reactor. With heating andstirring, the temperature rose to 108C over a 1% hour period. Thetemperature was lowered to 50C and 111.00 g (1.54 moles)beta-propiolactone added. Finally, 622.05 g (1.44 moles) chlorendicacidethylenimine salt were added. With further reaction, the temperaturerose to 165C over a period of eight hours. Vacuum was applied and, atabout 165C, the molten resin was transferred to 496 g styrene containing399 mg toluohydroquinone yielding 1940 g of 75.15 percent solution ofthe polyesteramide in styrene.

A sample was cured for 48 hours at room temperature using 0.2 percentcobalt naphthenate and 1.00 percent Lupersol DDM methyl ethyl ketoneperoxide solution. Final Acid Number was 41.0; Final Amine Number was3.8; Molecular Weight was 996; and 1mpact (2 lbs) was l5 inches.

EXAMPLE XIII Preparation of a Polyesteramide Using the Mono Salt ofChlorendic Acid and Ethylenimine; Maleic Anhydride; 1,6-Hexane Diol;Propylene Glycol; and Beta-Propiolactone Using the apparatus and generalprocedure as in Example VIII, 409.10 g (4.17 moles) maleic anhydride,386.70 g (3.27 moles) 1,6-hexane diol, and 84.18 g (1.10 moles)propylene glycol were charged under a nitrogen blanket to the reactor.Heating and stirring were commenced and the temperature rose to 106Cover a 1% hour period. The temperature was lowered to 68C and 75.17 g(1.04 moles) beta-propiolactone added. Immediately, 900.59 g (2.08moles) chlorendic acid-ethylenimine salt were added. Further reactionwas continued and the temperature rose to a maximum of 164C over aneight hour period. Vacuum (7 mm) was applied and, at about 160C, themolten resin was transferred to 1000 g styrene containing 830 mgbenzoquinone, 138 mg tertiary butyl catechol, and 138 mg methyl ether ofhydroquinone yielding 2620 g of a 61.82 percent solution of thepolyesteramide in styrene.

A sample was cured at about 25C for 48 hours using 0.4 percent cobaltnaphthenate and 2.0 percent Lupersol DDM methyl ethyl ketone peroxidesolution. Final Acid Number was 26.0; Final Amine Number was 6.3;Molecular Weight was 1358; and Impact (2 lbs), was 15 inches.

EXAMPLE XIV Fiber Glass Laminates Made with Polyesteramides Thepolyesteramide made in Example VIII is used as the binder in 12 inches X12 inches X A inch fiber glass laminates. One laminate is made using 12plies of type 181 glass cloth treated with methacrylatochromic chloridein isopropanol (DuPonts Volan A). Another laminate is made using 12plies of untreated type 181 glass cloth. The laminates are prepared bythe hand lay-up method. Curing of the resin is accomplished with 2.5percent Lupersol DDM initiator (60 percent methyl ethyl ketone peroxidein dimethyl phthalate) and 0.3 percent Uversol Cobalt Liquid 6 Percent",and is effected at about 25C in a press at 460 psi for 16 hours,followed by a post cure for eight hours in an oven at 150F.

It has been observed in our work that qualitatively polyesteramides havegood adhesion to glass. Generally, polyesters do not have good adhesionexcept to specially treated glass coated with a coupling agent such asDuPonts Volan A.

Comparison This comparative run illustrates the synthesis of theethyleneimine salt of oxalic acid of the formula:

II II The preparation of the salt of the above formula has been knownsince before the turn of the century and is described in 28 Berichte2929 (1895).

Using the general procedure of Example 1, 270.12 grams (3.00 moles)anhydrous oxalic acid was dissolved in 3000 ml dry acetone. To thissolution was with foaming, in a 98.2 percent yield.

Amine equivalent calculatedfor C H NO found 134.10

Carboxyl equivalent calculated for C H NO 66.55 found 73.13

The salt was then used to synthesize a polyesteramide. Thispolyesteramide has the undesirable property of being insoluble instyrene.

Using the reactor and general procedure described in Example VIII,205.04 grams (1.54 moles) of the salt, 151.04 grams (1.54 moles) ofmaleic anhydride, 123.04 grams (1.62 moles) propylene glycol and 250 mlxylene, were charged to the reactor. Using a nitrogen blanket thereactor was heated to l 19C with exotherming over a minute period.Heating was continued to 155C over a three hour period, at which timevacuum (6 mm Hg) was applied and the remaining glycol, water and xylenedistilled over. After 45 minutes the vacuum was removed and provisionswere made to transfer the molten polyesteramide into a styrene solutioncontaining 140 mg toluhydroquinone (200 ppm THO). Upon attempting todissolve the polyesteramide in styrene it was found that thepolyesteramide was totally insoluble in styrene at all temperatures upto C. At this temperature, attempts to effect solution were terminated.

The insolubility of this polyesteramide in styrene renders it useless inthe preparation of styrene cross-linked polyesteramides.

The principles, preferred embodiments and modes of operation of thepresent invention have been described in the foregoing specification.The invention which is intended to be protected herein, however, is notto be construed as limited to the particular forms disclosed, sincethese are to be regarded as illustrative rather than restrictive.Variations and changes may be made by those skilled in the art withoutdeparting from the spirit of the present invention.

We claim:

1. A polyesteramide containing repeating units represented by thestructural formula:

0 O O 0 O R is alkylene or alkylidene of from two to six carbon 01 (I312Cl atoms.

1 11 7. A polyesteramide of claim of the formula O H l l 9 W W W W 1)C--l -CRCl( -COIUOCR -COR OCCH;CH:

J L ,J L .1 L .l L J L .l L l R i wherein:

R7 R1 R is tetrachlorophenyle ne, tetrabromophenylene or W wherein R ishydrogen or lower alkyl; and

R is lower alkylene or lower alkylidene. R7 ls hydrogen or lower alkyl3. A polyesteramide according to claim 2 and con- R I sistingessentially of repeating units represented by the Rs triwt ra L L L orand wherein R has from 2 to 6 carbon atoms. wherein R is hydrogen orlower alkyl; and

4. A mixture of the polyesteramide of claim 3 and R is lower alkylene orlower alkylidene. styrene; 8. A polyesteramide of claim 6 consistingessentially 5.A glass fiber laminate contaimngabmdmg comp0 of repeatingunits represented by the structural forsition comprising thepolyesteramide ofclaim mula: V V

6. A polyesteramide comprising repeating units representedby thestructural formula 0 O 4 O O 1 O O O [alLRLi R%Ls i0 Laiolwlolcml J L Iwherein: wherein: R is selected from the group consisting of alkylene Ris of up to 15 carbon atoms, arylene of up to 12 carbon atoms, andaralkylene of up to 13 carbon atoms, wherein one or all of the hydrogenatoms 5 thereof can be substituted with one or more memwherein R ishydrogen or methyl; and bers selected fromthe group gongsting off L Q1 Ris lower alkylene or lower alkylidene having from Br, lower alkyl andlower alkoxy; 2 to 6 carbon atoms. R is aminoalkyleneoxy oroxyalkyleneamino 9. A mixture of the polyesteramide of claim 8 andwherein the alkylene portions contain from two to styrene. 15 carbonatoms; 10. A glass fiber-reinforced article containing a glass R isalpha-beta ethylenically unsaturated alkylidene fiber binder compositioncomprising the polyester of of from two to 34 carbon atoms; and claim 8.

2. A polyesteramide according to claim 1 wherein: R1 istetrachlorophenylene, tetrabromophenylene or
 3. A polyesteramideaccording to claim 2 and consisting essentially of repeating unitsrepresented by the structural formula:
 4. A mixture of thepolyesteramide of claim 3 and styrene.
 5. A glass fiber laminatecontaining a binding composition comprising the polyesteramide of claim3.
 6. A polyesteramide comprising repeating units represented by thestructural formula
 7. A polyesteramide of claim 6 of the formula
 8. Apolyesteramide of claim 6 consisting essentially of repeating unitsrepresented by the structural formula:
 9. A mixture of thepolyesteramide of claim 8 and styrene.
 10. A glass fiber-reinforcedarticle containing a glass fiber binder composition comprising thepolyester of claim 8.